TY - JOUR
T1 - Metal-mediated couplings of a diphosphastibolyl ring anion, [1,4,2-P2SbC2But2]-
T2 - Synthesis and characterisation of novel antimony-containing cage compounds
AU - Black, Steven J.
AU - Hibbs, David E.
AU - Hursthouse, Michael B.
AU - Jones, Cameron
AU - Malik, K. M.Abdul
AU - Thomas, Ryan C.
PY - 1997/11/21
Y1 - 1997/11/21
N2 - Two equivalents of the diphosphastibolyl ring anion, [1,4,2-P2SbC2But2]- reacted with FeCl3 to produce an antimony-containing cage compound, P4Sb2C4But4, via an oxidative coupling mechanism. This cage underwent an intramolecular rearrangement reaction when treated with [W(CO)5(thf)] (thf = tetrahydrofuran) to produce the complex [{W(CO)5}P4Sb2C4But 4], which X-ray crystallography shows to contain a three-membered PPC 'diphosphirane' ring. Treatment of cis-[PtCl2(PEt3)2] with 1 equivalent of [1,4,2-P2SbC2But2]- yielded the first example of a complex, trans-[PtCl(PEt3)2(η1-P2SbC 2But2], containing a solely η1-co-ordinated diphosphastibolyl ring. The crystal structure of this compound shows the heterocyclic ring to retain its aromaticity after co-ordination. Treatment of cis-[PtCl2(PEt3)2] with 2 equivalents of [1,4,2-P2SbC2But2]- initiated a ring-coupling reaction at the metal to give the novel cage complex cis-[Pt(PEt3)2(η2-P4Sb 2C4But4]. The molecular structure of the cage shows it to contain a highly strained, dianionic ligand, [P4Sb2C4But4] 2-, which chelates the platinum through antimony and phosphorus atoms. Unusual features in the 31P-{1H} NMR spectrum of the complex are described.
AB - Two equivalents of the diphosphastibolyl ring anion, [1,4,2-P2SbC2But2]- reacted with FeCl3 to produce an antimony-containing cage compound, P4Sb2C4But4, via an oxidative coupling mechanism. This cage underwent an intramolecular rearrangement reaction when treated with [W(CO)5(thf)] (thf = tetrahydrofuran) to produce the complex [{W(CO)5}P4Sb2C4But 4], which X-ray crystallography shows to contain a three-membered PPC 'diphosphirane' ring. Treatment of cis-[PtCl2(PEt3)2] with 1 equivalent of [1,4,2-P2SbC2But2]- yielded the first example of a complex, trans-[PtCl(PEt3)2(η1-P2SbC 2But2], containing a solely η1-co-ordinated diphosphastibolyl ring. The crystal structure of this compound shows the heterocyclic ring to retain its aromaticity after co-ordination. Treatment of cis-[PtCl2(PEt3)2] with 2 equivalents of [1,4,2-P2SbC2But2]- initiated a ring-coupling reaction at the metal to give the novel cage complex cis-[Pt(PEt3)2(η2-P4Sb 2C4But4]. The molecular structure of the cage shows it to contain a highly strained, dianionic ligand, [P4Sb2C4But4] 2-, which chelates the platinum through antimony and phosphorus atoms. Unusual features in the 31P-{1H} NMR spectrum of the complex are described.
UR - http://www.scopus.com/inward/record.url?scp=33748661118&partnerID=8YFLogxK
U2 - 10.1039/a704809b
DO - 10.1039/a704809b
M3 - Article
AN - SCOPUS:33748661118
SN - 0300-9246
SP - 4321
EP - 4326
JO - Dalton
JF - Dalton
IS - 22
ER -